Methods of using hop acids to control organisms

ABSTRACT

Methods of inhibiting the growth of organisms in aqueous systems such as papermaking systems, cooling systems and process waters of various types, comprises adding to the aqueous system a hop acid. Compositions comprising hop acids and papermaking suspensions or slurries, and/or additives, such as paper making additives, are also provided.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] This invention relates to the control of organisms, such asmicroorganisms, and in particular the inhibition of such organisms byemploying hop acids to inhibit the growth of such organisms and/or killsuch organisms. By way of illustration only, the invention hasparticular utility in aqueous systems, such as papermaking systems andprocess water systems, in particular systems that involve circulatingand/or recirculating water systems, such as cooling water systems, etc.

[0003] 2. Background of the Invention and Related Art

[0004] The control of organisms, and microorganisms in particular, hasbeen a continuing and troublesome problem in aqueous systems, such assystems that involve circulating and/or recirculating water systems,such as such as papermaking systems and process water systems, coolingwater systems, etc. Such microorganisms cause biofouling, such asdeposits of microorganisms or products (such as metabolic products) ofmicroorganisms that cause the formation of deposits such as films, matsand other deposits which can result in plugging of pores, reduced flow,reduced heat exchange rates, clogging, etc.

[0005] Slime formation, deposit formation and the formation offilamentous bacteria have been of particular concern, for example.

[0006] By way of non-limiting example only, filamentous bacteria (forexample, Sphaerotilus natans) are often the cause of deposits on papermachines and fouling in cooling systems. Many types of filamentousbacteria grow on submerged surfaces in single chains within structuresreferred to as “sheaths.” Sheaths are considered to be a protectivestructure, and as such, the structure promotes the survival of theorganism. For example, the sheath structure is thought to protect theorganism from biocides, because, for example, getting the biocide intothe protective structure poses a problem. Filamentous bacterial growthon submerged surfaces in paper process streams can contribute to theformation of large deposits consisting of cells and inert materials(particulates, fines, fiber, etc.) that become enmeshed in thefilaments. Long “stringers” of the filamentous bacteria as well as largeclumps of deposits can become dislodged and cause problems such asholes, other defects, and breaks in the paper. This, therefore, cancause significant increases in the cost of producing paper. Filamentousbacteria also cause problems in cooling towers. Submerged surfacesfouled with filamentous and other types of bacteria cause a reduction inthe efficiency of heat transfer, in cooling systems for example, as wellas other problems resulting from large amounts of biomass becomingdislodged and circulating within an industrial setting.

[0007] The control of such microorganisms is even more difficult in viewof the fact that many of the microorganisms which are the cause of suchproblems are resistant to attempts to control them, such as byinhibiting their growth and/or killing them. For example, microorgansimsthat pose problems in aqueous industrial systems, such as process watersand papermaking systems, are resistant to a broad spectrum of conditionsand materials, and thus are able to remain viable in a wide variety ofsuch conditions. Therefore, biocides have been employed in efforts tocontrol such microorganisms. However, conventional biocides areexpensive, are not sufficiently environmentally friendly, exhibit anundesirably broad spectrum of activity (i.e., they are not targeted tothe specific microorganisms desired to be killed), must be employed inrelatively large concentrations, and/or can be harmful and/or dangerousand/or even toxic to humans. Moreover, in aqueous systems or media inwhich the control of organisms is desired, the compatibility of thecompositions and methods employed are also a consideration. Accordingly,a biocide which is effective with regard to the foregoing and which doesnot exhibit the mentioned disadvantages is desired.

[0008] With respect to all of the foregoing, there has been a continuingneed for improvement.

[0009] It is known in the brewing industry that some hop acids caninhibit the growth of microorganisms that can cause spoilage in beer.For example, U.S. Pat. No. 5,082,975 discloses that the hop acid,hexahydrolupulone, can inhibit the growth of certain Lactobacillus. Thispatent further discloses that there has been speculation that hops mayhave helped control brew house bacterial infections due to the presenceof hop acids in the wort and beer. However, since the hop beta acids arenot found in beer, such control, if it indeed existed, was thought tohave been due to the hop alpha acids and iso-alpha acids. Beta acids areknown to be highly unstable, being oxidized in the boiling wort tobitter hulupones and by themselves to deteriorate in a matter of days orhours after crystallization. This lack of stability is now shown to beovercome by conversion to hexahydrolupulone (hexahydro beta acids).There is a vast excess of lupulone available as a result of beingdiscarded in the brewing process, making it a potentially inexpensiveraw material. U.S. Pat. No. 4,918,240 is a related patent to U.S. Pat.No. 5,082,975. Each of these patents is hereby incorporated by referenceas though set forth in full herein.

[0010] U.S. Pat. No. 5,455,038 discloses that the hop acids,tetrahydroisohummulone and hexahydrocolupulone (α and β hops,respectively), a product of the brewing industry, have been identifiedas compounds that can inhibit food born pathogens from the generaListeria, Staphylococcus, Bacillus, and Clostridium. In addition, U.S.Pat. No. 5,286,506 discloses that solid food products can be protectedfrom food pathogens, including Listeria monocytogenes, by incorporatingbeta-acids, which are extracted from hops, into such food products. U.S.Pat. No. 5,455,038 discloses the inhibition of Listeria with α and β hopacids. Each of these patents is hereby incorporated by reference asthough set forth in full herein.

[0011] Derivatives of the β-hydrogenated lupulones can inhibit or killcancer cells (WO 97/31630 and WO 98/11883) as well as antibioticresistant strains of Staphylococcus aureus, Mycobacterium tuberculosis,and Mycobacterium avian Complex or enterococcus (“Antimicrobial activityof the Semisynthetic Compound, Hexahydrocolupolone”, Stephan et al.,Journal of Antimicrobial Chemotherapy (1998) 41, 519-522). Each of thesedocuments is hereby incorporated by reference as though set forth infull herein. Additionally, α and β hop acids have been identified as atherapeutic agent for methicillin resistant Staphylococcus aureus(Japanese Patent document JP 9067250). This document is herebyincorporated by reference as though set forth in full herein.

[0012] U.S. Pat. No. 5,370,863 discloses that oral care compositionscontaining hop acids or their salts are effective in inhibiting Grampositive bacteria, including Streptococcus mutans, which can causeplaque or periodontal disease, which document is hereby incorporated byreference as though set forth in full herein. A representativecomposition is a toothpaste containing tetrahydroisohumulone.

[0013] Hop acids have been considered to be selective to Gram-positivebacteria. See, for example, WO 98/11883, incorporated by referenceabove.

SUMMARY OF THE INVENTION

[0014] The invention provides a method of controlling organisms, such asmicroorganisms, particularly bacteria, in aqueous systems or media, suchas papermaking systems and process water systems, in particular systemsthat involve circulating and/or recirculating water systems, such ascooling water systems, etc., which method employs materials which arereadily available from renewable resources and which are also effective.

[0015] The invention provides a method of controlling such organisms insuch aqueous systems which method employs materials which are relativelyinexpensive.

[0016] The invention provides a method of controlling such organisms insuch aqueous systems which method is effective against a wide variety ofmicroorganisms but which are also targeted to the microorganisms whichaffect such aqueous systems.

[0017] The invention provides a method of inhibiting the growth oforganisms in an aqueous system selected from a papermaking system, acooling system or a process water which process water does not contact afinal product; or combinations thereof, comprising adding to the aqueoussystem a hop acid.

[0018] Preferably, the hop acid comprises a member selected from α or βhop acids, and mixtures thereof.

[0019] In preferred embodiments, the method comprises adding a hop acidselected from one or more of a compound of Formula (I):

[0020] wherein “----” represents an optional double bond;

[0021] R₁ comprises a member selected from OH; and saturated, orunsaturated (containing from about 1 to about 5 double bonds), straight-or branched-chain alkyl or alkenyl of from about 1 to about 20 C atoms,more preferably from about 1 to about 10 C atoms and more preferablyfrom about 1 to about 5 C atoms;

[0022] R₂ comprises a member selected from —OH; ═O; —SH; ═S; andsaturated, or unsaturated (containing from about 1 to about 5 doublebonds), straight- or branched-chain alkyl or alkenyl of from about 1 toabout 20 C atoms, more preferably from about 1 to about 10 C atoms andmore preferably from about 1 to about 5 C atoms;

[0023] R₃ comprises a member selected from —OH; ═O; —SH and ═S; and—OOR, wherein R comprises a member selected from H and C_(n)H_(2n−1),where n is an integer of from about 2 to about 10, more preferably fromabout 2 to about 7, and more preferably from about 2 to about 5;

[0024] R₄ comprises a member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms,more preferably from about 1 to about 10 C atoms, and more preferablyfrom about 1 to about 5 C atoms; a ketone of from about 1 to about 20carbon atoms, more preferably from about 1 to about 10 carbon atoms, andmore preferably from about 1 to about 4 carbon atoms, an aldehyde of thegeneral formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10,more preferably from about 2 to about 7, and more preferably from about2 to about 5; and —OOR, wherein R comprises a member selected fromC_(n)H_(2n+1) wherein n is as defined previously, and H; and/or Formula(II):

[0025] wherein R₅ comprises a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10,more preferably from about 2 to about 7, and more preferably from about2 to about 5;

[0026] R₆ comprises a member selected from —OH, —SH, and —OOR, wherein Rcomprises a member selected from C_(n)H_(2n+1) where n is an integer offrom about 2 to about 10, more preferably from about 2 to about 7, andmore preferably from about 2 to about 5; and H; and

[0027] R₇ comprises a member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms,more preferably from about 1 to about 10 C atoms, and more preferablyfrom about 1 to about 5 C atoms;

[0028] R₈ comprises member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms,more preferably from about 1 to about 10 C atoms, and more preferablyfrom about 1 to about 5 C atoms; a ketone of from about 1 to about 20carbon atoms, more preferably from about 1 to about 10 carbon atoms, andmore preferably from about 1 to about 4 carbon atoms, an aldehyde of thegeneral formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10,more preferably from about 2 to about 7, and more preferably about 5;and/or Formula (III):

[0029] wherein R₉ comprises a saturated, or unsaturated (containing fromabout 1 to about 5 double bonds), straight- or branched-chain alkyl oralkenyl of from about 1 to about 20 C atoms, more preferably from about1 to about 10 C atoms and more preferably from about 1 to about 5 Catoms; and

[0030] R₁₀ comprises a member selected from a ketone of from about 1 toabout 20 carbon atoms, more preferably from about 1 to about 10 carbonatoms, and more preferably from about 1 to about 4 carbon atoms, analdehyde of the general formula C(O)H or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10,more preferably from about 2 to about 7, and more preferably from about2 to about 5; and/or Formula (IV):

[0031] wherein R₁₁ comprises a saturated, or unsaturated (containingfrom about 1 to about 5 double bonds), straight- or branched-chain alkylor alkenyl of from about 1 to about 20 C atoms, more preferably fromabout 1 to about 10 C atoms and more preferably from about 1 to about 5C atoms; and

[0032] R₁₂ comprises a member selected from a ketone of from about 1 toabout 20 carbon atoms, more preferably from about 1 to about 10 carbonatoms, and more preferably from about 1 to about 4 carbon atoms, analdehyde of the general formula C(O)H, or a ketone of theC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10,more preferably from about 2 to about 7, and more preferably from about2 to about 5.

[0033] Preferably R₄ comprises a substituent of the formula

[0034] wherein R₁₃ comprises a C₃-C₈ alkyl group.

[0035] Preferably R₁₃ comprises a member selected from —CH₂CH(CH₃)₂;—CH(CH₃)₂; and —CH(CH₃)₂CH₂CH₃.

[0036] Preferably the method comprises adding a hop acid which comprisesa member selected from hexahydrolupulone; hexahydrocolupulone;hexahydroadlupulone, and mixtures thereof.

[0037] Preferably the hop acid comprises hexahydrocolupulone.

[0038] Preferably R₈ comprises a substituent of the formula

[0039] wherein R₁₄ comprises a C₃-C₈ alkyl group.

[0040] Preferably R₁₄ comprises a member selected from CH₂CH(CH₃)₂;—CH(CH₃)₂; —CH₂)₂CH(CH₃)₂; —CH(CH₃)₂ CH₂CH₃. and mixtures thereof.

[0041] Preferably the hop acid comprises tetrahydroisohumulone.

[0042] The organism can comprise a microorganism selected fromGram-negative bacteria, Gram-positive bacteria, and mixtures thereof.

[0043] The microorganism can comprise a member selected fromSphaerotilus natans, Clostridium butyricum, Pseudomonas aeruginosa,Curtobacterium flaccumfaciens, Burkholderia cepacia, Pseudomonas glathi,Bacillus cereus, Bacillus maroccan us, Bacillus licheniformis, Bacillussphaericus, Bacillus subtilis, and mixtures thereof.

[0044] The microorganism can comprise a Gram-negative bacteria.

[0045] The microorganism can comprise a member selected from Altermonas,Aquaspirillum, Campylobacter, Helicobacter, Acinetobacter,Agrobacterium, Alcaligenes, Alteromonas, Flavobacterium, Pseudomonas,Xanthomonas, Mycoplasma, Methanococcus mixtures thereof.

[0046] The microorganism can comprise a Gram-positive bacteria.

[0047] The microorganism can comprise a member selected from Bacillus,Enterococcus, Planococcus, Staphylococcus, Streptococcus, Clostridium,Lactobacillus, Listeria, Actinomyces, Arthrobacter, Corynebacterium,Curtobacterium, Norcardia, Actinoplanes, Mycobacterium and mixturesthereof. mixtures thereof.

[0048] The aqueous system can comprise a papermaking system.

[0049] The aqueous system can comprise a process water. The aqueoussystem can comprise a cooling system.

[0050] The hop acid preferably is present in an amount of from about0.001 to about 1,000 ppm.

[0051] The hop acid is preferably present in an amount of from about 0.1to about 250 ppm.

[0052] The hop acid is preferably present in an amount of from about 0.1to about 100 ppm.

[0053] The hop acid is preferably added with a freezing pointdepressant.

[0054] The invention also comprises a method of inhibiting the growth oforganisms in a papermaking system, comprising adding to the papermakingsystem a hop acid in accordance with any of the foregoing definitions.

[0055] The invention also provides a composition comprising a hop acidin accordance with any of the foregoing definitions and a memberselected from a papermaking suspension, a defoamer, an alum, anadhesive, a paper mill coating, a pigment slurry, a starch, a pitchcontrol agent, a scale control agent, a sizing agent, and mixturesthereof.

[0056] Preferably, the papermaking suspension comprises a memberselected from refined or unrefined furnish stock; refined or unrefinedpulp; paper making furnish, and combinations thereof.

[0057] The invention also provides a cellulosic product comprising amember selected from paper and paper board.

[0058] The paper can comprise a member selected from stationery paper,paper towel and tissue paper.

BRIEF DESCRIPTION OF THE DRAWINGS

[0059] The present invention is further described in the detaileddescription which follows, in reference to the noted plurality ofdrawings by way of non-limiting examples of exemplary embodiments of thepresent invention, in which like reference numerals represent similarparts throughout the several views of the drawings, and wherein:

[0060]FIG. 1 illustrates the growth inhibition of S. natans by hop acidin accordance with the following examples; and

[0061]FIG. 2 illustrates results of experiments with hop acids in thetreatment of spore-forming bacteria.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0062] The present invention is based on the discovery that hop acidscan be employed to control organisms such as by inhibiting the growth ofand/or killing organisms including both Gram-positive and Gram-negativemicroorganisms. As used herein the terms “control of organisms” and“inhibition of organisms” is intended to include either or both of theinhibition of the growth of organisms and killing organisms, and theseterms should be interpreted as being interchangeable herein.

[0063] The invention is particularly directed to the control oforganisms in aqueous systems such as papermaking systems and processwater such as cooling water, as well as any other aqueous system. Asused herein “aqueous systems” and “aqueous media” are intended includeany part of the aqueous system in question and to include the additionof hop acid at any point within or external to the system, especially incases which result in a hop acid being present in a portion of theaqueous system. Thus, the invention is expressly intended to coversituations where the hop acid is added upstream of and/or downstream ofand/or directly and/or indirectly to the aqueous system in question.Moreover, the terms “aqueous systems” and “aqueous media” are intendedto cover any situation or environment in which water is present,including slurries and solutions as illustrative, non-limiting examples.

[0064] The methods of the invention are useful in treating any aqueoussystem or media in which it may be desired to inhibit the growth ofand/or kill organisms such as microorganisms. As discussed elsewhereherein, in some embodiments, the processes of the invention involveadding hop acids to aqueous systems which may come into direct contactwith final product, such as aqueous systems associated with papermaking.In other embodiments, the processes of the invention involve adding hopacids to aqueous systems which do not directly contact final product.Illustrative, non-limiting examples of aqueous systems which do notdirectly contact final product include recirculating process waters suchas cooling waters which may be separated by a final product by a barriersuch as a heat exchanger, etc.

[0065] Thus, “aqueous system” refers to industrial aqueous systems inaddition to papermaking systems and are intended to embrace any suchaqueous system wherein the water of the system, such as a process water,does not come into contact with the final product. Non-limiting examplesinclude cooling water systems, such as internal combustion enginecooling systems, power plant cooling systems; heat exchangers, includingradiator coolants, etc.; aqueous systems used in humidifiers; aqueoussystems used in heating, ventilating and air conditioning systems;swimming pool water; water used in spas; metal working fluids; petroleumproduction fluids including drilling muds; paint formulation;disinfectants and sanitizers; plastics processing systems; mixtures ofthe foregoing; and any other aqueous systems. Methods of the inventioncontrol organisms in such systems by adding a hop acid to thepapermaking system or other aqueous systems.

[0066] Any hop acid may be employed in the methods of the invention. Ithas been found that α and/or β hop acids are particularly suitable, suchas those of Formula (I), (II) (III) and (IV), above.

[0067] As used herein, whenever reference is made to a compound orcomponent, unless otherwise stated, it includes the individual compoundor component by itself as well as mixtures of the compound or component,unless otherwise excluded. Thus, for example, reference to hop acidsincludes the occurrence of a single hop acid and to mixtures of varioushop acids and mixtures with various other materials.

[0068] Further, when an amount, concentration, or other value orparameter, is given as a list of upper preferable values and lowerpreferable values, this is to be understood as specifically disclosingall ranges formed from any pair of an upper preferred value and a lowerpreferred value, regardless whether ranges are separately disclosed.

[0069] It is specifically contemplated that mixtures of compounds ofFormula (I) with other compounds of Formula (I) and mixtures ofcompounds of Formula (II) with other compounds of Formula (II), andmixtures of compounds of Formula (III) with other compounds of Formula(III), and mixtures of compounds of Formula (IV) with other compounds ofFormula (IV), as well as mixtures of compounds of Formulae (I), (II),(III) (IV), in any combination of one or more of such compounds ofFormulae (I), (II), (III) or (IV), can also be employed. Compounds ofFormulae (I) and (III) are predominately β hop acids (but also caninclude some α hop acids) and compounds of Formula (II) arepredominately α hop acids (but also can include some β hop acids).

[0070] Non-limiting examples of α hop acids include: humulone,isohumulone; cohumulone; adhumulone; tetrahydroisohumulone;tetrahydrodeoxyhumulone.

[0071] Non-limiting examples of β hop acids include lupulone;colupulone; hexahydrocolupoulone; and hexahydrolupulone.

[0072] Especially preferred hop acids of Formula (I) include thosewherein R₄ comprises

[0073] wherein R₁₃ comprises a member selected from (C₃-C₈) alkyl, suchas —CH₂CH(CH₃)₂; —CH(CH₃)₂; and —CH(CH₃)₂CH₂CH₃. Exemplary compounds aredisclosed in WO 98/11883, which is hereby incorporated by referenceherein in its entirety for its disclosure of such compounds and includehexahydrolupulone (R═—CH₂CH(CH₃)₂); hexahydrocolupoulone or “HHC”(R═CH(CH₃)₂); and hexahydroadlupulone (R═CH(CH₃)₂CH₂CH₃).Hexahydrocolupulone or “HHC” is a particularly preferred compound ofFormula (I).

[0074] Especially preferred hop acids of Formula (II) include thosewherein R₈ comprises

[0075] wherein R₁₄ is selected from (C₃-C₈) alkyl, such as —CH₂CH(CH₃)₂;—CH(CH₃)₂;

[0076] —CH₂)₂CH(CH₃)₂; and —CH(CH₃)₂ CH₂CH₃.

[0077] Particularly preferred compounds of Formula (II) include thosewherein R comprises —CH₂)₂CH(CH₃)₂, such as tetrahydroisohumulone. Ofthese, tetrahydroisohumulone is particularly preferred.

[0078] Particularly preferred compounds of Formula (III) includecohumulone.

[0079] Particularly preferred compounds of Formula (IV) includetetrahydrodeoxyhumulone as disclosed in U.S. Pat. No. 4,918,240, whichdocument is hereby incorporated by reference as though set forth in fullherein for this disclosure as well.

[0080] Further elucidation of the structure and nomenclature of many ofthe foregoing compounds of Formulae (I) and (II) may be found in“Investigation of Hop and Beer Bitter Acids by Coupling ofHigh-performance Liquid Chromatography to Nuclear Magnetic ResonanceSpectroscopy”, Pusecker et al., Journal of Chromatography a, 836 (1999),245-252, which is hereby incorporated by reference as though set forthin full herein.

[0081] In general, compounds of the foregoing Formulae I-IV which arewater soluble are preferred. Also in general, the fewer the number ofcarbon atoms in the “R” group substituents denoted with “n” above, themore soluble the resulting compound. In preferred embodiments, n is aninteger of from about 1 to about 10, more preferably from about 2 toabout 7 and more preferably about 2 to about 5.

[0082] Hop acids may be isolated and prepared in any suitable way bythose of ordinary skill in the art, such as those disclosed in thedocuments incorporated by reference above, which are also incorporatedby reference for their disclosures of how to prepare such hop acids.Among those incorporated by reference, WO 98/11883, U.S. Pat. No.4,918,240 and U.S. Pat. No. 5,082,975 are instructive. Hop acids usefulin accordance with the present invention may also be prepared inaccordance with the disclosure of U.S. Pat. No. 4,844,939 to TODD, Jr.,which document, as well as all documents cited therein, is herebyincorporated by reference as though set forth in full herein for theirdisclosure of how to prepare hop acids. For example, this patentdiscloses that refined, preisomerized hop extracts are available in thetrade as solutions made according to various U.S. Patents, such as U.S.Pat. Nos. 3,448,326, 3,798,332, 3,965,188 (Westerman et al); U.S. Pat.Nos. 3,949,092 and 3,973,052 (Mitchell); and U.S. Pat. Nos. 3,486,906and 4,002,683 (Todd), all of which documents are hereby incorporated byreference as though set forth in full herein. To overcome thedisadvantage of using artificial, organic solvents, the use of liquidand supercritical carbon dioxide for the extraction of hops has beenemployed. This art is described in Kruger (Monatsschrift fur Brauerei,33, Nr. 3), which document is hereby incorporated by reference as thoughset forth in full herein. Moreover, methods for the isomerization andseparation of the constituents of carbon dioxide hop extracts can alsoemploy organic solvents and/or adsorption/extraction processes (LanceU.S. Pat. No. 4,395,431, which document is hereby incorporated byreference as though set forth in full herein or Mueller, DeutscheAuslegeschrift No. 2920765 which document is hereby incorporated byreference as though set forth in full herein), or “salt out” impurities(Laws U.S. Pat. No. 4,298,626 which document is hereby incorporated byreference as though set forth in full herein), or remove them byfiltration using large amounts of adsorbent in dilute solution (BakerU.S. Pat. No. 4,247,183 which document is hereby incorporated byreference as though set forth in full herein), all of the foregoingbeing cited in U.S. Pat. No. 4,844,939 to TODD, incorporated byreference above.

[0083] The hop acids may preferably be employed in the form of anaqueous solution, such as disclosed in WO 98/11883, U.S. Pat. No.4,918,240 and U.S. Pat. No. 5,082,975 and the solutions can be preparedas disclosed therein, which documents are again specificallyincorporated by reference herein for this purpose.

[0084] Suitable hop acids are commercially available in the form of anaqueous solution under the trade name “HYDROHOPS” available fromWatertown Hops Company, 1224 American Way, Watertown, Wis., 53094.

[0085] It has been found that the aqueous solution under the trade name“HYDROHOPS” can be employed directly by being directly added to theaqueous system to be treated without the need for further formulation.

[0086] Propylene glycol, glycerine, similar stable alcohols and polyols,or mixtures thereof with or without water, may be substituted for thewater of the aqueous solution.

[0087] The solubility of the hop acids employed in the present inventioncan be affected by temperature. For example, the hop acids may besubject to crystallization at temperatures lower than room temperature.Therefore, it has been found particularly advantageous to employ one ormore freezing point depressive agents. The agents are preferablyemployed in any amount effective to lower the freezing point of thecomposition so as to inhibit cloudiness and/or crystallization of hopacid. Any freezing point depressive agent may employed and may bereadily selected by those of ordinary skill in the art. Examplesinclude:

[0088] Glycerol (glycerine); polyglycerols such as diglycerol,triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, and higheroligomers of glycerol;

[0089] Glycols, such as ethylene glycol, diethylene glycol, propyleneglycol, dipropylene glycol, tripropylene glycol, and higher oligomers ofglycols;

[0090] Polyglycol triols selected from glycerol propoxylate, glycerolethoxylate, and mixtures thereof;

[0091] Monohydric alcohols, which can range for example, from methylthrough C₅₀ alcohols, more preferably C₆-C₃₆, and may include, forexample, methanol, ethanol, isopropanol, butanol, isobutanol, amylalcohol, isoamyl alcohol, hexanol, isohexanol, heptanol, n-octanol,2-ethylhexanol, iso-octanol, n-nonanol, isononyl alcohol, n-decanol,isodecanol, n-lauryl alcohol, tridecanol, n-myristyl alcohol, n-cetylalcohol, isocetyl alcohol, n-stearyl alcohol, isostearyl alcohol,octyldodecanol, archidyl alcohol, capryl alcohol, oleyl alcohol,alcohols up through C₅₀, more preferably up through C₃₆, ethoxylatedand/or propoxylated versions of the above-described alcohols,phenoxyethanols, and ethoxylated and/or propoxylated versions of theabove-described alcohols, phenoxyethanols, and ethoxylated and/orpropoxylated nonyl phenols (numerous additional alcohols, includingmonohydric alcohols being readily selectable by those of ordinary skillin the art); and

[0092] other freezing point depressive actives, such as monohydricalcohol diester (used in the cosmetic and personal care industries),Triclosan (2,4,4′-trichloro-2′-hydroxyl diphenyl ether), alkyl glycolethers (dipropylene glycol methyl ether), salts (organic and inorganic)polyethylene glycols, alkyl carbitols, peptides (“antifreeze peptides”),glycopeptides (“antifreeze glycopeptides”), alkyl amines, etc.

[0093] In accordance with the invention, hop acids may be employed inany amount effective to control the organism, as by inhibiting thegrowth of and/or killing, organisms. In general, for the aqueous systemsreferenced herein, the hop acid should be employed in amounts of fromabout 0.001 to about 1,000 ppm, preferably from about 0.1 to about 250ppm, and more preferably from about 0.1 to about 100 ppm, based onamount of active ingredient (hop acid) in the aqueous system in questionon an as is basis.

[0094] It has surprisingly been found that the invention is suitable forcontrolling a wide variety of organisms, including microorganisms suchas Gram-negative as well as Gram-positive bacteria. It is particularlysurprising that hop acids can be employed to control Gram-negativemicroorgansims. Other microorganisms can be inhibited by the inventionas well, including dinoflagellattes, microalgae, microfungi, bacteria,protozoans or mixtures thereof. The invention is particularly effectivein controlling the vegetative form of microorganisms.

[0095] Examples of Gram-negative microorganisms which can be inhibitedby the methods of the invention include Genus Altermonas, GenusAquaspirillum, Genus Campylobacter, Genus Helicobacter, GenusAcinetobacter, Genus Agrobacterium, Genus Alcaligenes, Alteromonas,Genus Flavobacterium, Genus Pseudomonas, Genus Xanthomonas, GenusMycoplasma, Genus Methanococcus, and mixtures thereof.

[0096] Examples of Gram-positive microorganisms which can be inhibitedby the methods of the invention include Genus Bacillus, GenusEnterococcus, Genus Planococcus, Genus Staphylococcus, GenusStreptococcus, Genus Clostridium, Genus Lactobacillus, Genus Listeria,Genus Actinomyces, Genus Arthrobacter, Genus Corynebacterium, GenusCurtobacterium, Genus Norcardia, Genus Actinoplanes, Genus Mycobacteriumand mixtures thereof.

[0097] The invention is also effective against FamilyEnterobacteriaceae, including Genus Escherichia, Genus Enterobacter,Genus Klebsiella, and mixtures thereof, as well as Family Vibronacea,including Genus Aeromonas, Genus Vibrio and mixtures thereof.

[0098] The invention is also effective against other bacteria, includingGenus Desulfovibrio, Genus Thiobacterium and mixtures thereof.

[0099] Other microorganisms against which the invention is effective, aswell as species of the foregoing may be found in Bergey's Manual ofDeterminative Bacteriology, Holt et al., Williams & Wilkins, NinthEdition (1994) which document is hereby incorporated by reference asthough set forth in full herein. The sections: Group 2 (including page39), Group 3 (including page 71), Group 5 (including page 175), Group 12(including page 427), Group 14 (including page 477), Group 17 (includingpage 527), and Group 18 (including page 559) are also herebyincorporated by reference as though set forth in full herein for theirmore specific disclosure of such microorganisms.

[0100] Methods of the invention have been found particularly effectivein controlling microorganisms selected from Sphaerotilus natans,Clostridium butyricum, Pseudomonas aeruginosa, Curtobacteriumflaccumfaciens, Burkholderia cepacia, Pseudomonas glathi, Bacilluscereus, Bacillus maroccanus, Bacillus lichen iformis, Bacillussphaericus, Bacillus subtilis, and mixtures thereof.

[0101] Whether inhibition of growth or killing of a microorganism hasoccurred, and the extent to which it has occurred can be measured bythose of ordinary skill in the art, such as in accordance with theExamples below.

[0102] In accordance with the methods of the invention, hop acids may beadded to the aqueous system to be treated in any manner. In many casesthe method of the invention may be conducted by simply adding acommercially available solution of hop acids, such as HYDROHOPS directlyto the aqueous system to be treated. The hop acid may also be addedafter being diluted or added to other media to form an admixture orsolution, which admixture or solution may then be added to the aqueoussystem to be treated. Thus, the hop acid may be added by being added asa component to additives for papermaking or other aqueous systems, theformulation of which additives is otherwise well known to those ofordinary skill in the art.

[0103] Treatment of Papermaking Systems

[0104] The invention may be applied to any papermaking system at anypoint in the system and in any manner where additives are typicallyemployed and in any manner that additives used in the paper industry areemployed. Solutions, such as aqueous solutions of hop acids may beemployed directly and/or indirectly, or in admixture with anypapermaking additive, such as those papermaking additives discussedherein.

[0105] Non-limiting examples of suitable aspects for addition include:

[0106] Refined or unrefined furnish stock in stock tanks.

[0107] Pulp refining conducted in a refiner.

[0108] Refined pulp stored, ready for use in stock chests.

[0109] Paper making furnish drawn from stock chests.

[0110] The flow box, the point at which the paper making furnish flowsat a controlled rate onto the fourdrinier wire.

[0111] Or any combination of the foregoing, upstream of any of theforegoing locations, or any point in between such locations, or anyother suitable location, or combination of locations, concurrently or atdifferent times.

[0112] Preferably, hop acids in accordance with the invention may beemployed in the amounts discussed above.

[0113] When added to a papermaking composition such as a papermakingadditive or papermaking pulp or slurry, the hop acid can become acomponent of the resultant product. Thus, the invention also providescellulosic products such as paper and paper products comprising hopacids. The presence of hop acids in cellulosic products including paperand paper products provides advantages of effectively controllingorganisms in the aqueous systems associated with the production of suchproducts, while not posing safety, toxicity or related concerns, and/oradverse physiological reactions. This is of particular significance withrespect to cellulosic products comprising members selected fromstationery paper, paper towel and tissue paper.

[0114] Treatment of Other Process Waters

[0115] The invention may be applied to any process water system at anypoint in the system and in any manner where additives are typicallyemployed and in any manner that additives used in such industries areemployed. Non-limiting examples of suitable aspects for addition includeaddition at the normal fill opening of the system, incorporation with oras part of the original liquid added to the system, etc.

[0116] Any combination of the foregoing may be employed.

[0117] Compositions

[0118] As can be seen, the invention also comprises composition aspects.

[0119] Thus, as non-limiting examples, the invention also provides acomposition comprising a hop acid and an aqueous medium selected from apapermaking systems and other aqueous systems such as emulsions,adhesives, process waters, including cooling water systems, such asinternal combustion engine cooling systems, power plant cooling systems;heat exchangers, including radiator coolants, etc.; aqueous systems usedin humidifiers; aqueous systems used in heating, ventilating and airconditioning systems; swimming pool water; water used in spas; metalworking fluids; petroleum production fluids including drilling muds;paint formulation; disinfectants and sanitizers; plastics; mixtures ofthe foregoing; and any other aqueous systems.

[0120] Additional exemplary applications for such compositions areprovided in Disinfection, Sterilization, and Preservation, FourthEdition, Block, Lea & Febiger (1991), which is hereby incorporated byreference as though set forth in full herein, for its disclosure of suchapplications. Table 56-2 of this document is also expressly incorporatedby reference herein in its entirety.

[0121] The invention further provides a composition compositions whichare preserved for later addition to aqueous systems, such as additivesfor paper making and water treatment additives. Thus, the invention alsocomprises compositions comprising a hop acid and a paper making additiveselected from defoamers, alum, adhesives, paper mill coatings, pigmentslurries, starches, pitch control agents, scale control products, sizingagents (including alkyl ketene dimer sizing agents (AKD's), and mixturesthereof. Papermaking compositions in accordance with the inventioncomprise Non-limiting examples of suitable composition aspects:

[0122] Refined or unrefined furnish stock in stock tanks.

[0123] Pulp such as that in a refiner.

[0124] Refined pulp stored, ready for use in stock chests.

[0125] Paper making furnish drawn from stock chests.

[0126] The flow box, the point at which the paper making furnish flowsat a controlled rate onto the fourdrinier wire.

[0127] Or any combination of the foregoing, upstream of any of theforegoing locations, or any point in between such locations, or anyother suitable location, or combination of locations, concurrently or atdifferent times.

[0128] Details and optimization of routine components, formulations, anduse considerations can be found, for example, in Pulp and Paper,Chemistry and Chemical Technology, Casey, James P. (editor), J. Wiley,3d. edition (1980), the entire disclosure of which is herebyincorporated by reference, as though set forth in full herein for thispurpose.

[0129] Without further elaboration, it is believed that one skilled inthe art can, using the preceding description, utilize the presentinvention to its fullest extent.

[0130] The following preferred specific embodiments are, therefore, tobe construed as merely illustrative, and not limitative of the remainderof the disclosure in any way whatsoever. In the following examples, alltemperatures are set forth uncorrected in degrees Celsius; unlessotherwise indicated, all parts and percentages are by weight.

EXAMPLES Example 1 Control of S. natans

[0131] This example illustrates that a derivative of a naturallyoccurring compound in hops can control the growth of S. natans, afilamentous organism. The results of adding selected concentrations ofhop acids to cultures of S. natans are presented below. In thosestudies, individual flasks containing a dilute culture medium (e.g., CYGbroth, described in more detail below) were inoculated with differentstrains of S. natans (ATCC 15291 and ATCC 29329), and selectedconcentrations of hop acid (HYDROHOPS from Watertown Hops, diluted to10, 25, and 50 ppm tetrahydroisohumulone). The cultures were incubatedand, after 48 and 96 hours, the flasks were agitated, and a 1 ml sampleremoved for ATP measurement. The difference between untreated controlsand treated cultures yielded the percent inhibition. Specific protocolincluded the following:

[0132]S. natans (ATCC cultures 15291, 29329, and 13925) were grown onCYG broth which had the following composition: 0.5 g/l casitone, 1.0 g/lglycerol, and 0.1 g/l yeast extract. S. natans strains were grown in 50ml culture volumes in shake flasks on an orbital shaker at roomtemperature. Experiments were initiated by inoculating tests flasks withequal amounts of S. natans taken from 48 hour to 72 hour old brothcultures. Selected concentrations of the active were added to flaskscontaining S. natans. The control used in all experiments wereuntreated. The effect of hop acid on S. natans was quantitated using ATPmeasurements. ATP analysis was conducted using reagents and luminometerfrom Biotrace Ltd (Bridgend, U. K.). ATP extractions and measurementswere carried out as follows:

[0133] 1. Test cultures are repeatedly mixed with a 10 ml pipet to breakup flocs and yield a uniform suspension.

[0134] 2. 100 microliters of culture is combined with 100 microliters ofextractant in a test tube. The tube is then shaken and let stand at roomtemperature for 1 minute.

[0135] 3. 100 microliters of luciferase enzyme is added to the mixture,shaken and placed in the luminometer. A reading (relative lightunits—rlu), corresponding to the amount of ATP extracted is recorded.All data were generated using replicate extractions.

[0136] Data Analyses:

[0137] The rlu readings for each treated flask were normalized with thecontrol reading to yield a percent inhibition of growth.

[0138] The graph in FIG. 1 indicates that the I₅₀ value (theconcentration of active needed to inhibit 50% of the population) forboth strains of microorganisms is ca. 10 ppm.

Example 2 Inhibition of Clostridium butyricum

[0139] Investigation into the inhibition of anaerobic bacteria wasconducted with Clostridium butyricum in a disk diffusion assay. Separateα and β hop acids (HYDROHOPS) were employed. This microorganism wasfound to be very susceptible to the inhibitory properties the alpha hopacid, and not so susceptible with the beta hop acids. Screening data,shown in Table I, below, indicate no synergy between these two compoundsat equal concentrations between 0.1 to 1 mg/disk. These data can becorroborated with the aerobic Gram-positive bacteria data, shown inTable II. Further disk diffusion studies indicated a bacteriocidalactivity from 5 to 50 mg/disk, and bacteriostatic activity at 1 mg/disk(zones of inhibition are given in Table I below).

[0140] Organism: Clostridium butyricum (ATCC 3627)

[0141] Medium: Oxoid, Reinforced Clostridial Medium, (UNIPATH, Ltd.)

[0142] Experimental Procedures

[0143]Clostridum butyricum microorganism obtained from the American TypeCulture Collection (Strain # ATCC 3627), was transferred to fresh RCMagar (Oxoid, Reinforced Clostridial Medium from UNIPATH) 16 hours priorto initiation of the experiment.¹ BBL (blank paper discs (¼″ diameter,STN 31039, Becton Dickinson Microbiological Systems)) were sterilizedprior to loading with hop acid. Each sterile disk was loaded with hopacid at the desired concentration and allowed to air dry prior totransfer to anaerobic chamber. New RCM agar plates were inoculated withthe previously-streaked C. butyricum actively growing on RCM plates.This assures that the microorganisms were in a logarithmic growth phase.All disks were aseptically transferred to the plates, and the platesincubated at 35° C. for 48 hours. Clear zones known as “zones ofinhibition” were measured with a ruler and their values recorded after24 and 48 hours incubation. After 48 hours, the plates were removed fromthe anaerobic chamber and photographed. The data reported forClostridium butyricum represent the diameter of the zones of inhibition;the greater the cleared zone the more active the product or the higherthe concentration.

[0144] The results are shown in Table I, below.

[0145] It should be pointed out that these zones of inhibition indicatethat, in addition to inhibiting the growth of the microorganism, themicroorganisms were killed, since the zone remained clear. These resultsalso indicate that there is at least some degree of aqueous solubilityof the active ingredient, because, in order to result in a zone ofinhibition, the hop acid must have been soluble to at least some degree(or else the hop acid would not have migrated through the agar). TABLE IAlpha Hop Acid Beta Hop Acid Alpha//Beta Hop Acid Zone of Zone of Zoneof Concentration Inhibition (mm) Concentration Inhibition (mm)Concentration Inhibition (mm) (mg/disk) 24 hr 48 hr (mg/disk) 24 hr 48hr (mg/disk) 24 hr 48 hr 1000 23 23 1000 15 15 1000 21 21 500 23 23 50015 15 500 20 20 250 23 23 250 12 12 250 21 32 100 23 23 100 11 10 100 1616 50 20 24 50 none none 25 20 21 25 none none 10 18 19.5 10 none none 515 14.3 5 none none 4 15 13 4 none none 3 13 11.5 3 none none 2 12 12 2none none 1 10 10 1 none none

Example 3 Microtiter Assay

[0146] In examining the alpha and beta hops in a microtiter based assaywith both Gram-positive and Gram-negative bacteria using a syntheticwhite water solution, it was found that some of the Gram-negativebacteria were susceptible to the hop acids, but at a much higherconcentration (e.g., Pseudomonas aeruginosa). This screening evaluationindicated that these compounds, the alpha and beta hop acids, are veryeffective over a wide concentration range with a variety of differentmicroorganisms. This efficacy demonstrates that these compounds find ause not only in pulp and paper applications, but probably a wide varietyof water treatment applications (such as, cooling towers, etc.). Theresults are set forth in Table II, below. TABLE II Bacterial Strain pHHop Acid Time (hrs) I₅₀ (ppm) Klebsiella 5.5 Alpha 4 18.07 pneumonia24 >40 (ATCC 13883) 8.0 4 >40 24 >40 5.5 Beta 4 35.79 24 >40 8.0 4 >4024 >40 Pseudomonas 5.5 Alpha 4 0.357 aeruginosa 24 >2.5 (ATCC 15442) 7.24 >2.5 24 >2.5 8.0 4 >2.5 24 >2.5 5.5 Beta 4 0.036 24 >2.5 7.2 4 >2.524 >2.5 8.0 4 >2.5 24 >2.5 Curtobacterium 5.5 Alpha 4 0.447flaccumfaciens 24 0.837 (BPC 124A) 7.2 4 >2.5 24 >2.5 8.0 4 18.7224 >2.5 5.5 Beta 4 0.084 24 0.935 7.2 4 0.293 24 1.49 8.0 4 0.748 241.72 Burkholderia 5.5 Alpha 4 25.63 cepacia 24 >40 (BPC 216A) 8.0 4 >4024 >40 5.5 Beta 4 3.67 24 9.26 8.0 4 6.23 24 6.85 Pseudomonas 5.5 Alpha4 39.86 glathi 24 >40 (BPC 322B) 8.0 4 >40 24 >40 5.5 Beta 4 >40 24 >408.0 4 >40 24 4.41 Bacillus 5.5 Alpha 4 0.214 cereus 24 0.899 (ATCC14579) 8.0 4 >2.5 24 >2.5 5.5 Beta 4 0.033 24 0.230 8.0 4 0.404 24 0.758Bacillus 5.5 Alpha 4 0.535 maroccanus 24 1.66 (BPC 223A) 7.2 4 >2.524 >2.5 8.0 4 17.32 24 33.11 5.5 Beta 4 0.091 24 1.46 7.2 4 0.57924 >2.50 8.0 4 0.922 24 1.60 Bacillus 5.5 Alpha 4 0.281 licheniformis 240.513 (ATCC 12759) 8.0 4 >2.5 24 >2.5 5.5 Beta 4 0.026 24 0.324 8.0 40.257 24 0.734 Bacillus 5.5 Alpha 4 No growth sphaericus 24 No growth(ATCC 4525) 8.0 4 >2.5 24 >2.5 5.5 Beta 4 No growth 24 No growth 8.0 40.099 24 0.194 Bacillus 5.5 Alpha 4 0.479 subtilis 24 0.795 (ATCC 23059)8.0 4 >2.5 24 >2.5 5.5 Beta 4 0.026 24 0.09 8.0 4 0.175 24 0.116

Example 4 Effect of Hop Acid On Spores

[0147] Experimental: A preparation of spores of Bacillus cereus was usedfor the experiments. Spores were prepared by growing cultures of B.cereus in nutrient broth overnight at 37° C. Cultures were harvested bycentrifugation and resuspended in sterile distilled water. They werethen placed at 80° C. for 15 minutes. After heat treatment, sporepreparations were stored at 4° C. for at least 48 hours prior to use.

[0148] Tests of the effect of L-alanine and hop acid were conducted asfollows. Suspensions of B. cereus spores were added to sterile water toobtain a spore stock having a concentration of about 10⁴ to 10⁵spores/ml. The spore stock was then divided into 1.0 ml aliquots fortesting. L-alanine was supplied at concentrations of 1 or 2.5 mM. AfterL-alanine addition, spores were placed at 37° C. for one hour. AfterL-alanine treatment, hop acid (HYDROHOPS from Watertown Hops,Wisconsion) was added to the spores. After a 20 minute exposure, thespore samples were taken through a serial dilution and plated onnutrient agar medium. Plates were incubated at 37° C. overnight, andafter this period, colonies were counted.

[0149] The effect of L-alanine was assessed by comparing the platecounts to control spore preparations that were not exposed to L-alanine.To ensure that L-alanine had effectively induced germination sporesamples were treated with L-alanine and placed at 80° C. for 15 minutes.

[0150] Results: As shown in FIG. 2 and TABLE III, control samples A andB show that L-alanine did induce germination, however, killing ofgerminated cells by hop acid did not occur. This may be due to the factthat hop acid is a more “gentle” or slower acting killing agent thanheat or some of the other compounds tested with L-alanine (i.e.,dithiol, sulfone/quat blend, glutaraldehyde). The key to FIG. 2 is shownin TABLE III as follows: TABLE III Example No. L-alanine (mM) BiocidalTreatment CFU SD A 1 Heat - 80° C., 15 min. 72 6 B 2.5 Heat - 80° C., 15min. 85 1.4 C 0 Hop Acid (50 ppm) 220 9.5 D 0 Hop Acid (25 ppm) 180 8.2E 1.0 Hop Acid (50 ppm) 200 11.9 F 2.5 Hop Acid (50 ppm) 180 16.5 G 1.0Hop Acid (25 ppm) 176 34.5 H 2.5 Hop Acid (25 ppm) 205 14.3 I 0 Heat -80° C., 15 min. 162 13.4

Example 5 Antifungal Efficacy Study Using Hop Acid

[0151] A disk diffusion assay using hop acid treatments was used toevaluate the efficacy of controlling the growth of two fungalspecies—Aspergillus niger and Chaetomium globosum. The agar plates usedin the experiment were potato dextrose (PDA). Fungal spores were appliedas a lawn onto PDA prior to the addition of disks containing hop acid.The disk concentrations used in this experiment were 100, 200, 500, and1000 ppm.

[0152] Plates were incubated at 35° C., and observations made daily. Theexperiment was terminated after 8 days, and the results from this studyindicated that there was growth observed around each disk aftersporulation (i.e., no zones of inhibition). This indicated that the hopacid was ineffective in controlling the growth of these two fungi.

Conclusion

[0153] The foregoing examples indicate that hop acids may not beeffective against some spore-forming bacteria, but are effective againstvegetative forms of bacteria.

[0154] From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various usages andconditions.

What is claimed is:
 1. A method of inhibiting the growth of organisms inan aqueous system selected from a papermaking system, a cooling systemor a process water which process water does not contact a final product;or combinations thereof, comprising adding to the aqueous system a hopacid.
 2. The method of claim 1, wherein the hop acid comprises a memberselected from α or α hop acids, and mixtures thereof.
 3. The method ofclaim 1, wherein the hop acid comprises a member selected from acompound in accordance with one or more of the following formulae:

wherein “----” represents an optional double bond; R₁ comprises a memberselected from OH; and saturated, or unsaturated (containing from about 1to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; R₂ comprises a member selected from—OH; ═O; —SH; ═S; and saturated, or unsaturated (containing from about 1to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; R₃ comprises a member selected from—OH; ═O; —SH and ═S; and —OOR, wherein R comprises a member selectedfrom H and C_(n)H_(2n+1), where n is an integer of from about 2 to about10; R₄ comprises a member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms; aketone of from about 1 to about 20 carbon atoms, a ketone of the generalformula C(O)H or C(O)C_(n)H_(2n+1), where n is an integer of from about2 to about 10; and —OOR, wherein R comprises a member selected fromC_(n)H_(2n+1) wherein n is an integer of from about 2 to about 10, andH; and/or:

wherein R₅ comprises a ketone of the general formula C(O)C_(n)H_(2n+1),where n is an integer of from about 2 to about 10,; R₆ comprises amember selected from —OH, —SH, and —OOR, wherein R comprises a memberselected from C_(n)H_(2n+1) where n is an integer of from about 2 toabout 10; and H; and R₇ comprises a member selected from saturated orunsaturated (containing from about 1 to about 5 double bonds), straight-or branched-chain alkyl or alkenyl of from about 1 to about 20 C atoms;R₈ comprises member selected from saturated or unsaturated (containingfrom about 1 to about 5 double bonds), straight- or branched-chain alkylor alkenyl of from about 1 to about 20 C atoms; an aldehyde of thegeneral formula C(O)H or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10;and/or:

wherein R₉ comprises a saturated, or unsaturated (containing from about1 to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; and R₁₀ comprises a member selectedfrom a ketone of from about 1 to about 20 carbon atoms an aldehyde ofthe general formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1); where n is an integer of from about 2 to about 10;and/or:

wherein R₁₁ comprises a saturated, or unsaturated (containing from about1 to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; and R₁₂ comprises a member selectedfrom a ketone of from about 1 to about 20 carbon atoms, an aldehyde ofthe general formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about
 10. 4.The method of claim 3, wherein R₄ comprises a substituent of the formula

wherein R₁₃ comprises a C₃-C₈ alkyl group.
 5. The method of claim 4,wherein R₁₃ comprises a member selected from —CH₂CH(CH₃)₂; —CH(CH₃)₂;and —CH(CH₃)₂CH₂CH₃.
 6. The method of claim 5, wherein the hop acidcomprises a member selected from hexahydrolupulone; hexahydrocolupulone;hexahydroadlupulone, and mixtures thereof.
 7. The method of claim 6,wherein the hop acid comprises, hexahydrocolupulone.
 8. The method ofclaim 3, wherein R₈ comprises a substituent of the formula

wherein R₁₄ comprises a C₃-C₈ alkyl group.
 9. The method of claim 8,wherein R₁₄ comprises a member selected from CH₂CH(CH₃)₂; —CH(CH₃)₂;—CH₂)₂CH(CH₃)₂; —CH(CH₃)₂ CH₂CH₃. and mixtures thereof.
 10. The methodof claim 9, wherein the hop acid comprises tetrahydroisohumulone. 11.The method of claim 1, wherein the organism comprises a microorganismselected from Gram-negative bacteria, Gram-positive bacteria, andmixtures thereof.
 12. The method of claim 11, wherein the microorganismcomprises a member selected from Sphaerotilus natans, Clostridiumbutyricum, Pseudomonas aeruginosa, Curtobacterium flaccumfaciens,Burkholderia cepacia, Pseudomonas glathi, Bacillus cereus, Bacillusmaroccanus, Bacillus licheniformis, Bacillus sphaericus, Bacillussubtilis, and mixtures thereof.
 13. The method of claim 11, wherein themicroorganism comprises a Gram-negative bacteria.
 14. The method ofclaim 13, wherein the microorganism comprises a member selected fromAltermonas, Aquaspirillum, Campylobacter, Helicobacter, Acinetobacter,Agrobacterium, Alcaligenes, Alteromonas, Flavobacterium, Pseudomonas,Xanthomonas, Mycoplasma, Methanococcus mixtures thereof.
 15. The methodof claim 11, wherein the microorganism comprises a Gram-positivebacteria.
 16. The method of claim 15, wherein the microorganismcomprises a member selected from Bacillus, Enterococcus, Planococcus,Staphylococcus, Streptococcus, Clostridium, Lactobacillus, Listeria,Actinomyces, Arthrobacter, Corynebacterium, Curtobacterium, Norcardia,Actinoplanes, Mycobacterium and mixtures thereof. mixtures thereof. 17.The method of claim 1, wherein the aqueous system comprises apapermaking system.
 18. The method of claim 1, wherein the aqueoussystem comprises a process water.
 19. The method of claim 1, wherein theaqueous system comprises a cooling system.
 20. The method of claim 1,wherein the hop acid is present in an amount of from about 0.001 toabout 1,000 ppm.
 21. The method of claim 20, wherein the hop acid ispresent in an amount of from about 0.1 to about 250 ppm.
 22. The methodof claim 21, wherein the hop acid is present in an amount of from about0.1 to about 100 ppm.
 23. The method of claim 1, wherein the hop acid isadded with a freezing point depressant.
 24. The method of claim 17,wherein the hop acid comprises a member selected from α or β hop acids,and mixtures thereof.
 25. The method of claim 17, wherein the hop acidcomprises a member selected from a compound in accordance with one ormore of the following formulae:

wherein “----” represents an optional double bond; R₁ comprises a memberselected from OH; and saturated, or unsaturated (containing from about 1to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; R₂ comprises a member selected from—OH; ═O; —SH; ═S; and saturated, or unsaturated (containing from about 1to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; R₃ comprises a member selected from—OH; ═O; —SH and ═S; and —OOR, wherein R comprises a member selectedfrom H and C_(n)H_(2n+1), where n is an integer of from about 2 to about10; R₄ comprises a member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms; aketone of from about 1 to about 20 carbon atoms, a ketone of the generalformula C(O)H or C(O)C_(n)H_(2n+1), where n is an integer of from about2 to about 10; and —OOR, wherein R comprises a member selected fromC_(n)H_(2n+1) wherein n is an integer of from about 2 to about 10, andH; and/or:

wherein R₅ comprises a ketone of the general formula C(O)C_(n)H_(2n+1),where n is an integer of from about 2 to about 10,; R₆ comprises amember selected from —OH, —SH, and —OOR, wherein R comprises a memberselected from C_(n)H_(2n+1) where n is an integer of from about 2 toabout 10; and H; and R₇ comprises a member selected from saturated orunsaturated (containing from about 1 to about 5 double bonds), straight-or branched-chain alkyl or alkenyl of from about 1 to about 20 C atoms;R₈ comprises member selected from saturated or unsaturated (containingfrom about 1 to about 5 double bonds), straight- or branched-chain alkylor alkenyl of from about 1 to about 20 C atoms; an aldehyde of thegeneral formula C(O)H or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10;and/or:

wherein R₉ comprises a saturated, or unsaturated (containing from about1 to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; and R₁₀ comprises a member selectedfrom a ketone of from about 1 to about 20 carbon atoms an aldehyde ofthe general formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10;and/or:

wherein R₁₁ comprises a saturated, or unsaturated (containing from about1 to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; and R₁₂ comprises a member selectedfrom a ketone of from about 1 to about 20 carbon atoms, an aldehyde ofthe general formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10.26. The method of claim 25, wherein R₄ comprises a substituent of theformula

wherein R₁₃ comprises a C₃-C₈ alkyl group.
 27. The method of claim 26,wherein R₁₃ comprises a member selected from —CH₂CH(CH₃)₂; —CH(CH₃)₂;and —CH(CH₃)₂CH₂CH₃.
 28. The method of claim 27, wherein the hop acidcomprises a member selected from hexahydrolupulone; hexahydrocolupulone;hexahydroadlupulone, and mixtures thereof.
 29. The method of claim 28,wherein the hop acid comprises, hexahydrocolupulone.
 30. The method ofclaim 25, wherein R₈ comprises a substituent of the formula

wherein R₁₄ comprises a C₃-C₈ alkyl group.
 31. The method of claim 30,wherein R comprises a member selected from CH₂CH(CH₃)₂; —CH(CH₃)₂;—CH₂)₂CH(CH₃)₂; —CH(CH₃)₂ CH₂CH₃. and mixtures thereof.
 32. The methodof claim 31, wherein the hop acid comprises tetrahydroisohumulone. 33.The method of claim 17, wherein the organism comprises a microorganismselected from Gram-negative bacteria, Gram-positive bacteria, andmixtures thereof.
 34. The method of claim 33, wherein the microorganismcomprises a member selected from Sphaerotilus natans, Clostridiumbutyricum, Pseudomonas aeruginosa, Curtobacterium flaccumfaciens,Burkholderia cepacia, Pseudomonas glathi, Bacillus cereus, Bacillusmaroccanus, Bacillus licheniformis, Bacillus sphaericus, Bacillussubtilis, and mixtures thereof.
 35. The method of claim 34, wherein themicroorganism comprises Sphaerotilus natans.
 36. The method of claim 34,wherein the microorganism comprises Clostridium butyricum.
 37. Themethod of claim 34, wherein the microorganism comprises Pseudomonasaeruginosa.
 38. The method of claim 34, wherein the microorganismcomprises Curtobacterium flaccumfaciens.
 39. The method of claim 34,wherein the microorganism comprises Burkholderia cepacia.
 40. The methodof claim 34, wherein the microorganism comprises Pseudomonas glathi. 41.The method of claim 34, wherein the microorganism comprises Bacilluscereus.
 42. The method of claim 34, wherein the microorganism comprisesBacillus maroccanus.
 43. The method of claim 34, wherein themicroorganism comprises Bacillus licheniformis.
 44. The method of claim34, wherein the microorganism comprises Bacillus sphaericus.
 45. Themethod of claim 34, wherein the microorganism comprises Bacillussubtilis.
 46. The method of claim 17, wherein the hop acid is present inan amount of from about 0.001 to about 1,000 ppm.
 47. The method ofclaim 46, wherein the hop acid is present in an amount of from about 0.1to about 250 ppm.
 48. The method of claim 47, wherein the hop acid ispresent in an amount of from about 0.1 to about 100 ppm.
 49. Acellulosic product produced by the process of claim
 17. 50. Thecellulosic product of claim 49, comprising a paper product.
 51. A methodof inhibiting the growth of organisms in an aqueous system selected fromcooling water systems; aqueous systems used in humidifiers; aqueoussystems used in heating, ventilating and air conditioning systems;swimming pool water; water used in spas; metal working fluids; petroleumproduction fluids; paint formulation; plastics processing systems; andmixtures of the foregoing; comprising adding to the aqueous system a hopacid.
 52. The method of claim 51, wherein the hop acid comprises amember selected from α or β hop acids, and mixtures thereof.
 53. Themethod of claim 51, wherein the hop acid comprises a member selectedfrom a compound in accordance with one or more of the followingformulae:

wherein “----” represents an optional double bond; R₁ comprises a memberselected from OH; and saturated, or unsaturated (containing from about 1to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; R₂ comprises a member selected from—OH; ═O; —SH; ═S; and saturated, or unsaturated (containing from about 1to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; R₃ comprises a member selected from—OH; ═O; —SH and ═S; and —OOR, wherein R comprises a member selectedfrom H and C_(n)H_(2n+1), where n is an integer of from about 2 to about10; R₄ comprises a member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms; aketone of from about 1 to about 20 carbon atoms, a ketone of the generalformula C(O)H or C(O)C_(n)H_(2n+1), where n is an integer of from about2 to about 10; and —OOR, wherein R comprises a member selected fromC_(n)H_(2n+1) wherein n is an integer of from about 2 to about 10, andH; and/or:

wherein R₅ comprises a ketone of the general formula C(O)C_(n)H_(2n+1),where n is an integer of from about 2 to about 10; R₆ comprises a memberselected from —OH, —SH, and —OOR, wherein R comprises a member selectedfrom C_(n)H_(2n+1) where n is an integer of from about 2 to about 10;and H; and R₇ comprises a member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms; R₈comprises member selected from saturated or unsaturated (containing fromabout 1 to about 5 double bonds), straight- or branched-chain alkyl oralkenyl of from about 1 to about 20 C atoms; an aldehyde of the generalformula C(O)H or a ketone of the general formula C(O)C_(n)H_(2n+1),where n is an integer of from about 2 to about 10; and/or:

wherein R₉ comprises a saturated, or unsaturated (containing from about1 to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; and R₁₀ comprises a member selectedfrom a ketone of from about 1 to about 20 carbon atoms an aldehyde ofthe general formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10;and/or:

wherein R₁₁ comprises a saturated, or unsaturated (containing from about1 to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; and R₁₂ comprises a member selectedfrom a ketone of from about 1 to about 20 carbon atoms, an aldehyde ofthe general formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10.54. The method of claim 53, wherein R₄ comprises a substituent of theformula

wherein R₁₃ comprises a C₃-C₈ alkyl group.
 55. The method of claim 54,wherein R₁₂ comprises a member selected from —CH₂CH(CH₃)₂; —CH(CH₃)₂;and —CH(CH₃)₂CH₂CH₃.
 56. The method of claim 55, wherein the hop acidcomprises a member selected from hexahydrolupulone; hexahydrocolupulone;hexahydroadlupulone, and mixtures thereof.
 57. The method of claim 56,wherein the hop acid comprises, hexahydrocolupulone.
 58. The method ofclaim 53, wherein R₈ comprises a substituent of the formula

wherein R₁₄ comprises a C₃-C₈ alkyl group.
 59. The method of claim 58,wherein R₁₄ comprises a member selected from CH₂CH(CH₃)₂; —CH(CH₃)₂;—CH₂)₂CH(CH₃)₂; —CH(CH₃)₂ CH₂CH₃. and mixtures thereof.
 60. The methodof claim 59, wherein the hop acid comprises tetrahydroisohumulone. 61.The method of claim 53, wherein the organism comprises a microorganismselected from Gram-negative bacteria, Gram-positive bacteria, andmixtures thereof.
 62. The method of claim 61, wherein the microorganismcomprises a member selected from Sphaerotilus natans, Clostridiumbutyricum, Pseudomonas aeruginosa, Curtobacterium flaccumfaciens,Burkholderia cepacia, Pseudomonas glathi, Bacillus cereus, Bacillusmaroccanus, Bacillus licheniformis, Bacillus sphaericus, Bacillussubtilis, and mixtures thereof.
 63. The method of claim 61, wherein themicroorganism comprises Sphaerotilus natans.
 64. The method of claim 61,wherein the microorganism comprises Clostridium butyricum.
 65. Themethod of claim 61, wherein the microorganism comprises Pseudomonasaeruginosa.
 66. The method of claim 61, wherein the microorganismcomprises Curtobacterium flaccumfaciens.
 67. The method of claim 61,wherein the microorganism comprises Burkholderia cepacia.
 68. The methodof claim 61, wherein the microorganism comprises Pseudomonas glathi. 69.The method of claim 61, wherein the microorganism comprises Bacilluscereus.
 70. The method of claim 61, wherein the microorganism comprisesBacillus maroccanus.
 71. The method of claim 61, wherein themicroorganism comprises Bacillus licheniformis.
 72. The method of claim61, wherein the microorganism comprises Bacillus sphaericus.
 73. Themethod of claim 61, wherein the microorganism comprises Bacillussubtilis.
 74. The method of claim 53, wherein the hop acid is present inan amount of from about 0.001 to about 1,000 ppm.
 75. The method ofclaim 74, wherein the hop acid is present in an amount of from about 0.1to about 250 ppm.
 76. The method of claim 74, wherein the hop acid ispresent in an amount of from about 0.1 to about 100 ppm.
 77. Acomposition comprising a hop acid and a member selected from apapermaking suspension, a defoamer, an alum, an adhesive, a paper millcoating, a pigment slurry, a starch, a pitch control agent, a scalecontrol agent, a sizing agent, and mixtures thereof.
 78. The compositionof claim 77, wherein the hop acid comprises a member selected from α orβ hop acids, and mixtures thereof.
 79. The composition of claim 77,wherein the hop acid comprises a member selected from a compound inaccordance with one or more of the following formulae:

wherein “----” represents an optional double bond; R₁ comprises a memberselected from OH; and saturated, or unsaturated (containing from about 1to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; R₂ comprises a member selected from—OH; ═O; —SH; ═S; and saturated, or unsaturated (containing from about 1to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; R₃ comprises a member selected from—OH; ═O; —SH and ═S; and —OOR, wherein R comprises a member selectedfrom H and C_(n)H_(2n+1), where n is an integer of from about 2 to about10; R₄ comprises a member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms; aketone of from about 1 to about 20 carbon atoms, a ketone of the generalformula C(O)H or C(O)C_(n)H_(2n+1), where n is an integer of from about2 to about 10; and —OOR, wherein R comprises a member selected fromC_(n)H_(2n+1) wherein n is an integer of from about 2 to about 10, andH; and/or:

wherein R₅ comprises a ketone of the general formula C(O)C_(n)H_(2n+1),where n is an integer of from about 2 to about 10; R₆ comprises a memberselected from —OH, —SH, and —OOR, wherein R comprises a member selectedfrom C_(n)H_(2n+1) where n is an integer of from about 2 to about 10;and H; and R₇ comprises a member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms; R₈comprises member selected from saturated or unsaturated (containing fromabout 1 to about 5 double bonds), straight- or branched-chain alkyl oralkenyl of from about 1 to about 20 C atoms; an aldehyde of the generalformula C(O)H or a ketone of the general formula C(O)C_(n)H_(2n+1),where n is an integer of from about 2 to about 10; and/or:

wherein R₉ comprises a saturated, or unsaturated (containing from about1 to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; and R₁₀ comprises a member selectedfrom a ketone of from about 1 to about 20 carbon atoms an aldehyde ofthe general formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10;and/or:

wherein R₁₁ comprises a saturated, or unsaturated (containing from about1 to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; and R₁₂ comprises a member selectedfrom a ketone of from about 1 to about 20 carbon atoms, an aldehyde ofthe general formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10.80. The composition of claim 79, wherein R₄ comprises a substituent ofthe formula

wherein R₁₃ comprises a C₃-C₈ alkyl group.
 81. The composition of claim80, wherein R₁₃ comprises a member selected from —CH₂CH(CH₃)₂;—CH(CH₃)₂; and —CH(CH₃)₂CH₂CH₃.
 82. The composition of claim 81, whereinthe hop acid comprises a member selected from hexahydrolupulone;hexahydrocolupulone; hexahydroadlupulone, and mixtures thereof.
 83. Thecomposition of claim 82, wherein the hop acid comprises,hexahydrocolupulone.
 84. The composition of claim 83, wherein R₈comprises a substituent of the formula

wherein R₁₄ comprises a C₃-C₈ alkyl group.
 85. The composition of claim84, wherein R₁₄ comprises a member selected from CH₂CH(CH₃)₂; —CH(CH₃)₂;—CH₂)₂CH(CH₃)₂; —CH(CH₃)₂ CH₂CH₃. and mixtures thereof.
 86. Thecomposition of claim 77, wherein the papermaking suspension comprises amember selected from refined or unrefined furnish stock; refined orunrefined pulp; paper making furnish, and combinations thereof.
 87. Acellulosic product comprising a hop acid and cellulosic fibers.
 88. Thecellulosic product of claim 87, wherein the hop acid comprises a memberselected from α or β hop acids, and mixtures thereof.
 89. The of claim87, wherein the hop acid comprises a member selected from a compound inaccordance with one or more of the following formulae:

wherein “----” represents an optional double bond; R₁ comprises a memberselected from OH; and saturated, or unsaturated (containing from about 1to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; R₂ comprises a member selected from—OH; ═O; —SH; ═S; and saturated, or unsaturated (containing from about 1to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; R₃ comprises a member selected from—OH; ═O; —SH and ═S; and —OOR, wherein R comprises a member selectedfrom H and C_(n)H_(2n+1), where n is an integer of from about 2 to about10; R₄ comprises a member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms; aketone of from about 1 to about 20 carbon atoms, a ketone of the generalformula C(O)H or C(O)C_(n)H_(2n+1), where n is an integer of from about2 to about 10; and —OOR, wherein R comprises a member selected fromC_(n)H_(2n+1) wherein n is an integer of from about 2 to about 10, andH; and/or:

wherein R₅ comprises a ketone of the general formula C(O)C_(n)H_(2n+1),where n is an integer of from about 2 to about 10; R₆ comprises a memberselected from —OH, —SH, and —OOR, wherein R comprises a member selectedfrom C_(n)H_(2n+1), where n is an integer of from about 2 to about 10 ;and H; and R₇ comprises a member selected from saturated or unsaturated(containing from about 1 to about 5 double bonds), straight- orbranched-chain alkyl or alkenyl of from about 1 to about 20 C atoms; R₈comprises member selected from saturated or unsaturated (containing fromabout 1 to about 5 double bonds), straight- or branched-chain alkyl oralkenyl of from about 1 to about 20 C atoms; an aldehyde of the generalformula C(O)H or a ketone of the general formula C(O)C_(n)H_(2n+1),where n is an integer of from about 2 to about 10; and/or:

wherein R₉ comprises a saturated, or unsaturated (containing from about1 to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; and R₁₀ comprises a member selectedfrom a ketone of from about 1 to about 20 carbon atoms an aldehyde ofthe general formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10;and/or:

wherein R₁₁ comprises a saturated, or unsaturated (containing from about1 to about 5 double bonds), straight- or branched-chain alkyl or alkenylof from about 1 to about 20 C atoms; and R₁₂ comprises a member selectedfrom a ketone of from about 1 to about 20 carbon atoms, an aldehyde ofthe general formula C(O)H, or a ketone of the general formulaC(O)C_(n)H_(2n+1), where n is an integer of from about 2 to about 10.90. The cellulosic product of claim 89, wherein R₄ comprises asubstituent of the formula

wherein R₁₃ comprises a C₃-C₈ alkyl group.
 91. The cellulosic product ofclaim 90, wherein R₁₃ comprises a member selected from —CH₂CH(CH₃)₂;—CH(CH₃)₂; and —CH(CH₃)₂CH₂CH₃.
 92. The cellulosic product of claim 91,wherein the hop acid comprises a member selected from hexahydrolupulone;hexahydrocolupulone; hexahydroadlupulone, and mixtures thereof.
 93. Thecellulosic product of claim 92, wherein the hop acid comprises,hexahydrocolupulone.
 94. The cellulosic product of claim 93, wherein R₈comprises a substituent of the formula

wherein R₁₄ comprises a C₃-C₈ alkyl group.
 95. The cellulosic product ofclaim 94, wherein R₁₄ comprises a member selected from CH₂CH(CH₃)₂;—CH(CH₃)₂; —CH₂)₂CH(CH₃)₂; —CH(CH₃)₂ CH₂CH₃. and mixtures thereof. 96.The cellulosic product of claim 97, comprising a member selected frompaper and paper board.
 97. The cellulosic product of claim 96 whereinthe paper comprises a member selected from stationery paper, paper toweland tissue paper.